CN107376989A - A kind of synthesis of Cu AEI molecular sieve catalysts and application - Google Patents
A kind of synthesis of Cu AEI molecular sieve catalysts and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The invention discloses a kind of Cu AEI Zeolite synthesis and application, using pyrroles/pyrrolidines material as organic formwork agent, it is silicon source and silicon source with FAU type Si-Al molecular sieves, other silicon sources can be combined, alkali source forms mixed sols, dynamic crystallization synthesizes AEI structure molecular screens, then other cations in the metallic salt and AEI of soluble Cu are swapped, obtains Cu AEI molecular sieves.Slurries are mixed to form with binding agent afterwards, are coated on porous regular carrier material, available for tail gas NOx selective catalytic reduction (SCR) catalyst.This catalyst provided by the invention can be applied on the gas reduction containing NOx that moving source and stationary source are discharged very well, can meet the standard requirement of exhaust emissions very well.
Description
Technical field
The present invention relates to a kind of synthesis of Cu-AEI molecular catalysts sieve and its apply, specifically Cu-AEI zeolites point
Son sieve, which is coated on porous regular material, is prepared as SCR catalyst, for the processing of tail gas clean-up containing NOx, belongs to inorganic material
Field.
Background technology
AEI structure molecular screens have the 3 D pore canal system of big cage, can form three-dimensional open-framework, hole by 8 yuan of rings
Footpath sizeWith CHA molecular sieves seemingly, cage size can reach its basket structure comprising diameterSpheroid.Difference
Adjacent double hexatomic rings of CHA structure are in spatially parallel junction in the two neighboring double six-membered ring structures connected with four-membered ring
Structure, and two adjacent double hexatomic rings are symmetrical in minute surface in AEI structures.Such structure difference causes eight yuan in AEI structures
Annular distance road has less aperture, and its catalytic activity is higher, and anti-carbon performance is more excellent.AEI Si-Al molecular sieves and sial phosphorus molecule
Sieve structure is respectively specifically using SSZ-39 and SAPO-18 as representative.The AEI molecular sieves of ion exchange or carried metal active component are urged
Agent, selective reduction (SCR) activity of uniqueness is shown, has good reduction treatment performance to nitrogen oxides (NOx),
Extensive concern is caused.
Nitrogen oxides (NOx) can cause a series of environmental problems such as photochemical fog, acid rain and greenhouse effects, seriously endanger
The health of victimization class, and with the increase of vehicles number and developing rapidly for industry, NOx discharge is increasing, will
Cause the severe exacerbation of ecology and environment.Thus, it is very urgent to eliminate NOx pollution problems.At present, NOx, which dominates control technology, is
NH3 SCRs (NH3-SCR), its key are to select the catalyst of excellent performance, and this will determine whole catalytic reaction
The success or failure of system.
Usual SCR catalyst is typically to have crystal structure using zeolite as what carrier, load SCR activity component were prepared
Molecular sieve；Zeolite is the silicon aluminate crystal material with quite regular pore size, such as β zeolites, Y zeolites, X boiling
Stone, faujasite, modenite, erionite, ZSM-5, ZSM-8, ZSM-11, ZSM-12 zeolite etc., these zeolites can be with
The metal exchanges such as Cu, Fe, Mn, Ag, V, Ti, Co, or zeolite is in itself containing metals such as some Cu, Fe.But it is above-mentioned
The metal-modified zeolite catalyst known can only be in narrower humidity province during ammine selectivity catalytic reduction nitrous oxides
The purification of nitrogen oxides is carried out in the range of domain, the NOx purifying properties for all not having high activity below 200 DEG C, hydrothermal stability
Difference, activity is relatively low under cryogenic conditions.
ZSM-5 and beta-molecular sieve have many shortcomings in the application.Their easy dealuminzations in high-temperature water Heat Ageing, lead
Cause acid reduction, particularly Cu/ β and Cu/ZSM-5 catalyst.β and ZSM-5 base catalyst is also influenceed by hydrocarbon, and hydrocarbon is compared with low temperature
The lower absorption of degree on a catalyst, and is oxidized with the rise of catalyst system and catalyzing temperature, releases substantial amounts of heat, catalyst is caused
Pyrolytic damage.When applied to automotive diesel, this problem is especially serious, because in cold start-up, a large amount of hydrocarbon can be adsorbed onto
On catalyst.β and ZSM-5 molecular sieve are also easy to because of hydrocarbon and coking.These low activity of molecular sieve catalysts are due to molecular sieve
Skeleton structure stability is poor, causes structure to destroy under the conditions of dramatic temperature conversion, metal active constituent is easily assembled, and reduces
The decentralization at metal ion activity center.
The CHA type molecular sieves that Cu is exchanged, such as the hydrothermal stability and SCR that Cu-SSZ-13 and Cu-SAPO-34 have had
Catalytic activity.Compared with ZSM-5, microcellular structure is included in CHA molecular sieves, and single monokaryon Cu can be adjusted2+Species, this is right
Hydrothermal aging and sulfur poisoning are more resistant.This kind of CHA types molecular sieve catalyst also has good activity and to the high of N2
Selectivity, turn into the most potential catalyst of discharged nitrous oxides in control exhaust gas from diesel vehicle.But SAPO-34 molecular sieves
Even required further improvement in hydrothermal durability and stability, and the template required for SSZ-13 Zeolite synthesis is expensive,
Synthesis cycle is grown, and low temperature and high temperature light-off performance are even insufficient.
AEI structure molecular screens provided by the invention have better hydrothermal stability and wider light-off performance window temperature
Spend (200~500 DEG C), possess good low temperature and high temperature light-off performance, have more suitable pore passage structure, beneficial to NOx molecules
Diffusion, strengthen the attachment of metal copper ion, reduce it by hydrothermal and produce the possibility of aggregation.
The content of the invention
It is an object of the present invention to provide a kind of AEI type molecular sieve catalysts of Cu loads, for explosive motor, combustion gas wheel
The waste gas such as machine, fire coal or oil-fired power generating NOx catalysis reduction (SCR) processing, improves hydrothermal stability and light-off performance.
In a particular embodiment, this method is used for the waste gas containing NOx for handling lean-burn internal combustion engine to the present invention, such as
The waste gas containing NOx of diesel engine, lean bum gasoline engine or the engine energized by liquefied petroleum gas or natural gas.
Molecular sieve catalyst of the present invention can also be used for handling the gas from the industrial process such as refined, from essence
Refine the gas containing NOx of heater and boiler, stove, chemical process industry (CPI), coke oven, municipal waste processing unit and incinerator etc..
Nitrogen oxides (NOx), including multiple compounds, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), three oxygen
Change phenodiazine (N2O3), dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) etc..
The present invention provides a kind of Cu-AEI molecular sieve catalysts and preparation method thereof, it is characterised in that：Using pyrroles/pyrroles
Alkanes material is silicon source and silicon source with FAU type Si-Al molecular sieves, can combine other silicon sources, alkali source shape as organic formwork agent
Into mixed sols, crystallization synthesis AEI type molecular sieves, load on AEI type molecular sieves, prepare using Ni metal as metallic promoter agent
Cu-AEI molecular sieve catalysts are obtained, are then mixed into slurries with binding agent, loads on porous regular material, may be used as
NOx SCRs (SCR) catalyst.
The molecule mol ratio of silica and aluminum oxide in AEI molecular sieves of the present invention is 15~300, Cu contents
It is 0.5~5.0wt% of Cu-AEI molecular sieve catalyst gross masses.
Cu-AEI molecular sieve catalysts preparation method of the present invention includes：
(1) by silicon source (SiO2Calculate), silicon source (Al2O3Calculate), alkali lye (Na2O calculate) and organic formwork agent (OSDA) press
According to Na2O:SiO2:Al2O3:OSDA:H2O=0.1~0.5:1.0:0.0033~0.083:0.05~0.5:10~50 mole
Ratio carries out being mixed into colloidal sol shape；
(2) mixture in (1) is transferred in crystallizing kettle and enters Mobile state and divide temperature section crystallization, first paragraph crystallization temperature
It is 120~150 DEG C to spend section, and crystallization time is 12~72 hours；Second segment crystallization temperature section is that 170~200 DEG C of crystallization times are
12~96 hours.
(3) molecular sieve that (2) crystallization obtains is reclaimed, then with copper ion salt in the model of pH value of solution=5.0~7.0
In enclosing, room temperature degassing process under negative pressure, then dried 4~24 hours at 60~100 DEG C, then roasted under normal pressure at 450~550 DEG C
Burn 2~8 hours, obtain Cu-AEI molecular sieves.
AEI Zeolite synthesis method of the present invention, silicon source can be selected from white carbon, Ludox, waterglass, alkyl silicon
It is one or more in acid esters, macro porous silica gel, silochrom, Kiselgel A, Type B silica gel and tlc silica gel.
AEI Zeolite synthesis method of the present invention, silicon source are selected from the Si-Al zeolite of FAU structures, including X and Y zeolites.
AEI Zeolite synthesis method of the present invention, organic formwork agent come from pyrroles/pyrrolidines material, including 1-
Hydroxyl -3,4- dimethyl pyrrolidine -2,5- diketone, the thio sulphur of 1- epoxide -2,2,5,5- tetramethylpyrrolidi-e -3- methylmethanes
Acid, 1- epoxide -3- carboxyl -2,2,5,5- tetramethylpyrrolidi-es, 1,2,2,5,5- pentamethyls pyrrolidines, 1- (4- ethyls -3,5- two
Methyl isophthalic acid H- pyrroles -2- bases)-ethyl ketone, 2,3,4,5- tetramethyls pyrroles, 1- isopropyl -2,3,4,5- tetramethyls pyrroles, 3,5-
Dimethyl -2- pyrrole aldehydes, 3,4,5- trimethyl -1H- pyrroles -2- methyl formates, 3,4,5- trimethyl -1H- pyrroles's -2- formic acid
Ethyl ester, 3- carboxyl -2,2,5,5- tetramethylpyrrolidi-e 1- oxygen radicals.
In method of the present invention, soluble copper salt is a kind of or several in copper nitrate, copper chloride, copper acetate or copper sulphate
Kind, the concentration of copper ion is 0.1~1.5mol/L in copper salt solution.
Cu-AEI of the present invention mixes with binding agent to be coated on porous regular carrier material, and binding agent can be that silicon is molten
It is one or more in glue, waterglass, boehmite, Alumina gel.
Porous regular material of the present invention includes honeycombed, board-like shape or corrugated regular carrier material, material choosing
From cordierite, alph-alumine, carborundum, aluminium titanates, silicon nitride, zirconium oxide, mullite, spodumene, alumina silica-oxygen
Change magnesium, zirconium silicate or sheet metal；The cellular of the preferred porous cordierite of carrier flows through type monolith carrier, and its bearing capacity is 170
~270g/L.
Cascade System of the present invention and include diesel oxidation catalyst, nitrogen base reductant in a manner of fluid communication
Source and SCR catalyst, the waste gas comprising NOx and reducing agent is set to be contacted with carbon monoxide-olefin polymeric, by least a portion of the NOx
Optionally it is reduced into N2And H2O。
The source of the nitrogenous reducing agent can be ammonia in itself, hydrazine or any suitable ammonia precursor, including urea, carbonic acid
It is one or more in ammonium, aminoquinoxaline, ammonium hydrogen carbonate or ammonium formate.
SCR catalyst of the present invention is coated in the honeybee on honeycomb fashion wall-flow filter or flow type material all in one piece or extruded
Nest body, washcoat of the AEI molecular sieve catalysts that transition metal exchanges for load on the substrate.
The tail gas containing NOx is preferably the waste gas stream of vehicular emission, more preferably obtained from the useless of lean-combustion engine
Air-flow, even more preferably diesel exhaust stream.
The method of the air-flow of the processing comprising NOx, wherein before the catalyst and the air flow contacts, with NOx
Measure as 100 weight %, its NO2 content is based upon 80 weight % or less, wherein preferably comprising 5~70 weight %, more preferably
10~60 weight %, more preferably 15~55 weight %, even more preferably 20~50 weight % NO2 contents.
The molecular sieve catalyst of the present invention can be coated in suitable base material single piece, or is configured to extrusion type catalysis
Agent, but be preferred in catalyst coat.
In certain embodiment of the present invention, molecular sieve catalyst (is had many flat coated in circulation monolithic devices base material
Capable passage aisle passes axially through the cellular integral catalyst carrier structure of whole part) or monolithic devices filter base material
Such as on wall-flow filter.
Certain aspects of the invention provide a kind of catalytic activation coating.Include the activation of AEI catalyst described here
Coating is preferably solution, suspension or slurry.Suitable coating includes face coat, the coating penetrated into a part of substrate, oozes
Enter coating or its certain combination of substrate.
The most frequently used substrates design of can be applied to two kinds of catalyst is tabular and cellular.Preferable substrate, particularly
For the substrate of Mobile solution, including the flow type material all in one piece with so-called honeycomb-like geometry, its include it is multiple it is adjacent,
Parallel passage, the passage be both ends open and it is usual extend to exit face from the inlet face of substrate, and produce high table
Area and volume ratio.For some applications, cellular flow type material all in one piece preferably has a high hole density, and e.g., from about 600~800
Hole/square inch, and/or average inner wall thickness is about 0.18~0.35mm, preferably from about 0.20~0.25mm.For it is some other
Using cellular flow type material all in one piece preferably has about 150~600 holes/square inch, more preferably from about 200~400 holes/square English
Very little lower well densities.
By the present invention in that by the use of the organic matter of the cheap pyrroles of cost or pyrrolidines as template, not only reduce
AEI Zeolite synthesis costs, and also assures that the requirement of crystallinity.
Catalyst in embodiment of the present invention, which is shown in much broader temperature window, obtains high conversion rate of NOx.Improve
The temperature range of transformation efficiency can be about 150~650 DEG C, preferably 200~500 DEG C, more preferably 200~450 DEG C, or most notable
It is preferred that 200~400 DEG C.In these temperature ranges, after reducing atmosphere, or even exposed to reducing atmosphere and high temperature
Transformation efficiency after (such as up to 850 DEG C) may be greater than 55% to 100%, more preferably greater than 90% efficiency, even
More preferably greater than 95% efficiency.
Brief description of the drawings
Below in conjunction with the accompanying drawings and embodiment the invention will be further described：
The XRD of AEI molecular sieves prepared by Fig. 1 embodiment of the present invention 1；
The SEM figures of AEI molecular sieves prepared by Fig. 2 embodiment of the present invention 1；
Embodiment
Embodiment of the present invention and caused effect, but the guarantor of the present invention are further illustrated by embodiment and comparative example
Shield scope is not limited to the content listed by embodiment.
Embodiment 1
(1) AEI zeolites (AEI types molecular sieve) are synthesized：
Will quantitative waterglass (Na2O：7.44wt%, SiO2：27.40wt%) it is added to organic formwork agent 1- hydroxyls -3,4-
The aqueous solution (the concentration of dimethyl pyrrolidine -2,5- diketone：In 25wt%), it is sufficiently stirred, then adding HY zeolites, (silica alumina ratio is
5.38, there is provided silicon source and part silicon source), NaOH particle (purity is sequentially added：96wt%), it is abundant to add deionized water for supplement
Stirring.Gained mixed serum in sealing container at room temperature in continuously stirring 2 hours, until all raw materials are well mixed, have with
Lower mole composition mixed sols mol ratio be：
Na2O：SiO2：Al2O3：OSDA：H2O=0.16：1.0：0.0752：0.15：15.0；
Gained solid mixture is moved toIn lining 2000ml hydrothermal crystallizing kettles, and stirred under 60rpm speed
Mix, 140 DEG C of crystallization 24 hours, be then warming up to 170 DEG C of crystallization 48 hours.After crystallization is complete, product cools down rapidly, by taking out
Filter separation, washing to pH value are to be calcined 4 hours at being dried 12 hours and 540 DEG C at 8.0~9.0,120 DEG C, you can obtain AEI
Molecular screen primary powder；
(2) copper is modified AEI molecular sieves：It is 0.2mol/L that the molecular screen primary powder 10.0g for taking step (1) to synthesize, which is added to concentration,
Cu (NO3)2·3H2In the O aqueous solution, into above-mentioned solution, dropwise addition dust technology adjusts its pH to 6.5, is inserted after stirring resistance to
In heat container, and it is put into together in the drier with pressure-reducing valve；With vavuum pump by the pressure in drier be extracted into 10Torr with
After lower, room temperature carries out the degassing process of 1 hour, is then warming up to 90 DEG C of conditions and dries 12 hours, by dried sample just
The lower 500 DEG C of temperature calcinations of normal atmospheric pressure 4 hours；Obtain described copper and be modified AEI molecular sieves, prepared according to icp analysis result
Catalyst in, copper (II) ion accounts for the 2.9% of molecular sieve catalyst gross weight, i.e. copper load capacity is 2.9wt%, and Na ions contain
Amount is less than 200ppm.
(3) the copper modified molecular screen for taking 15g steps (2) to obtain, with 6.71g Ludox (SiO2Content：30.0wt%) and
16.90g deionized waters are well mixed, and are fabricated to solid content and are 44.1wt% catalyst slurry, and it is applied by infusion process
On the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of the cordierite system of overlaying on, blown off with compressed air
Unnecessary slurry droplet, dry 24 hours at 110 DEG C, then same condition coats 2 times, is made after being calcined 2h under the conditions of 500 DEG C
It is standby into SCR catalyst, load capacity on regular material is 216g/L (quality of regular material weightening divided by regular material after roasting
Occupied spatial volume, follow-up embodiment and comparative example are mutually similar on the definition of load capacity), for obtained SCR catalysis
Agent is designated as A, and related preparation parameter and substance classes are as shown in Tables 1 and 2.
Embodiment 2
The process of synthesis AEI Si-Al molecular sieves is analogous to embodiment 1, except that mixed sols in step (1)
Mol ratio, organic formwork agent species, the species of silicon source, FAU zeolite types and silica alumina ratio, crystallization temperature and crystallization time etc.,
15g copper is taken to be modified AEI molecular sieves in the species of Cu salt and the load capacity of Cu ions, and (3) step in step (2), with 6.24g
Alumina gel (Al2O3Content：20.0wt%) it is well mixed with 26.80g deionized waters, it is urging for 33.8wt% to be fabricated to solid content
Agent slurries, by infusion process coated on the regular material of cordierite.Design parameter is as shown in Table 1 and Table 2 in the present embodiment.
Embodiment 3
The process of synthesis AEI Si-Al molecular sieves is analogous to embodiment 1, except that mixed sols in step (1)
Mol ratio, organic formwork agent species, the species of silicon source, FAU zeolite types and silica alumina ratio, crystallization temperature and crystallization time etc.,
15g copper is gone to be modified AEI molecular sieves in the species of Cu salt and the load capacity of Cu ions, and (3) step in step (2), with 6.40g
Boehmite (Al2O3Content：70.9wt%) it is well mixed with 27.80g deionized waters, it is 39.7wt% to be fabricated to solid content
Catalyst slurry, by infusion process coated on the regular material of cordierite..Design parameter such as Tables 1 and 2 institute in the present embodiment
Show.
Embodiment 4
The process of synthesis AEI Si-Al molecular sieves is analogous to embodiment 1, except that mixed sols in step (1)
Mol ratio, organic formwork agent species, the species of silicon source, FAU zeolite types and silica alumina ratio, crystallization temperature and crystallization time etc.,
15g copper is gone to be modified AEI molecular sieves, 6.60g silicon in the species of Cu salt and the load capacity of Cu ions, and (3) step in step (2)
Colloidal sol (SiO2Content：30.0wt%) it is well mixed with 26.60g deionized waters, is fabricated to the catalysis that solid content is 35.2wt%
Agent slurries, by infusion process coated on the regular material of cordierite.Design parameter is as shown in table 1 and table 2 in the present embodiment.
Embodiment 5
The process of synthesis AEI Si-Al molecular sieves is analogous to embodiment 1, except that mixed sols in step (1)
Mol ratio, organic formwork agent species, crystallization temperature and crystallization time etc., in addition using the FAU zeolites of high silica alumina ratio as silicon and aluminum source,
Silicon source is not used in addition；15g copper is gone to be modified in the species of Cu salt and the load capacity of Cu ions, and (3) step in step (2)
AEI molecular sieves, 6.10g Ludox (SiO2Content：30.0wt%) it is well mixed with 25.60g deionized waters, is fabricated to and contains admittedly
The catalyst slurry for 36.0wt% is measured, by infusion process coated on the regular material of cordierite..Design parameter in the present embodiment
As shown in Table 1 and Table 2.
Embodiment 6~18
The process of synthesis AEI Si-Al molecular sieves is analogous to embodiment 1, except that mixed sols in step (1)
Mol ratio, organic formwork agent species, the species of silicon source, FAU zeolite types and silica alumina ratio, crystallization temperature and crystallization time etc.,
Other silicon source is not provided in embodiment 6, embodiment 11 and embodiment 16；The species of Cu salt and Cu ions is negative in step (2)
In carrying capacity, and (3) step on regular material SCR catalyst load capacity.Design parameter such as Tables 1 and 2 institute in the present embodiment
Show.
Table 1
Table 2
Comparative example 1
17.0g SB powder is dissolved in the NaOH aqueous solution that 50.0g concentration is 50wt%, then added thereto
200.0g white carbons are sufficiently mixed.By N, N, N- trimethyl adamantane ammonium hydroxide (TMADa+) aqueous solution (concentration 25wt%)
It is slowly added in the mixture, while is mixed.It is slowly added to 80.0g deionized waters and gained mixture is sufficiently mixed 1
Hour.A mole composition for synthetic mixture is：
0.21Na2O：SiO2：0.0286Al2O3：0.18TMADa+：26.8H2O
Then gained gel is transferred in stainless steel cauldron in 170 DEG C of crystallization 168 hours, after the completion of reaction, will produced
Thing is washed with deionized, and 12h is dried at 120 DEG C, at 540 DEG C 4 hours of roasting obtain SSZ-13 molecular screen primary powders.
10g SSZ-13 molecular screen primary powders are added to the Cu (NO that 100g concentration is 0.3mol/L3)2·3 H2The O aqueous solution
In, into above-mentioned solution, dropwise addition dust technology adjusts its pH to 5.8, stirs.After stopping stirring 1 hour, when SSZ-13 zeolites
Supernatant is fallen in siphon after sedimentation.Reuse fresh copper nitrate solution to exchange once, finally filtering, deionized water washing exchange
SSZ-13 zeolites afterwards.Under 10 Torr low pressure, after 90 DEG C are dried 12 hours, then in the lower 500 DEG C of temperature of normal ambient pressure
The lower roasting of degree 4 hours, obtains described copper and is modified SSZ-13 molecular sieve powders.According to icp analysis result, copper (II) ion accounts for point
2.5%, the Na ion concentrations of sub- sieve catalyst gross weight are less than 200ppm.
The copper for taking 15g to obtain is modified SSZ-13 molecular sieves, the Ludox (30wt%SiO with 5.56g2) and 22.80g go
Ionized water is well mixed, and is fabricated to the catalyst slurry that solid content is 38.44wt%, and it is blue or green coated in violet by infusion process
On cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) made of stones, unnecessary slurries are blown off with compressed air
Drop, dry at 110 DEG C 12 hours, then coat a slurries again again, SCR catalyst is prepared into after being calcined 2h at 500 DEG C,
The catalyst loadings measured on regular material are 228.4g/L, to be designated as VS-1.
Comparative example 2
Weigh 13.59g boehmites and be dissolved in 108.0g deionized waters and stir at room temperature, afterwards by 23.24g phosphorus
Acid dihydride ammonium, which is added thereto, continues uniform stirring 2 hours, slurries is filtered, 110 DEG C of dry 4h, and 500 DEG C of roasting 2h obtain phosphorus aluminium
Dry glue thing, then crush and obtain≤100 μm of particle.
By above-mentioned gained whole particulate matter and 0.61g chromatographic silica gels, 54.0g deionized waters, 7.70g morpholines and 1.815g
Tripropylamine is mixed, and uniform mixed gel thing is transferred in stainless steel autoclave, 600 revs/min of speed stirrings
After 0.5h, crystallization 24h is stirred at 150 DEG C, then be warming up to crystallization 48h at 180 DEG C.Crystallization is water-cooled rapidly stopping after terminating
Crystallization, product can obtain molecular screen primary powder after filtering separation, deionized water washing, 120 DEG C of drying 24h.Then will divide
Son, which sieves former powder and is put into, to be warming up to 550 DEG C of constant temperature calcining 4h and obtains the crystal powder of white in roaster, surveyed by X-ray diffraction
Must be SAPO-34 molecular sieves.
10g SAPO-34 original powder is added to the Cu (NO that 100g concentration is 0.2mol/L3)2·3H2In the O aqueous solution, to
Dust technology is added dropwise in above-mentioned solution and adjusts its pH to 4.0, stirs.After stopping stirring 1 hour, when SAPO-34 molecular sieves sink
Supernatant is fallen in siphon after drop.Reuse fresh copper nitrate solution to exchange once, after finally filtering, deionized water washing exchange
SAPO-34 molecular sieves.Under 10Torr low pressure, after 90 DEG C are dried 12 hours, then in the lower 500 DEG C of temperature of normal ambient pressure
The lower roasting of degree 4 hours, obtains described copper modified SAPO-34 molecular sieve powder.According to icp analysis result, copper (II) ion accounts for
2.5%, the Na ion concentrations of molecular sieve catalyst gross weight are less than 200ppm.
The copper modified SAPO-34 molecular sieve that 15g is obtained is taken, the Ludox (30wt%SiO with 5.48g2) and 26.6g go
Ionized water is well mixed, and is fabricated to the catalyst slurry that solid content is 35.35wt%, and it is blue or green coated in violet by infusion process
On cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) made of stones, unnecessary slurries are blown off with compressed air
Drop, dry at 110 DEG C 12 hours, then coat a slurries again again, SCR catalyst is prepared into after being calcined 2h at 500 DEG C,
The catalyst loadings measured on regular material are 234.1g/L, to be designated as VS-2.
Comparative example 3
The beta-molecular sieve selective reduction catalyst that a kind of copper is modified, is prepared by following methods：
(1) the NaOH aqueous solution is added into cataloid (silica quality content is 30wt%), is sufficiently stirred
Al (NO are added afterwards3)3·9H2The aqueous solution of the O aqueous solution and TEAOH (TEAOH content 35wt%), the reaction after being sufficiently stirred mix
Compound, the mol ratio of raw material are：Na2O： Al2O3：SiO2：TEAOH：H2O is 21.0：1.0：300.0：150.0：4000.0；
(2) above-mentioned reactant mixture is put into polytetrafluoroethylcontainer container, closed self-generated pressure, heated under the conditions of 155 DEG C
72h；Then be centrifuged, wash, 120 DEG C of dryings how long 12h, be calcined 4 at 550 DEG C under normal atmosphere pressure
Hour removes removing template；With nSiO in icp analysis product2： nA12O3Mol ratio be 29：1, the XRD analysis product is with BEA
The beta-molecular sieve of type structure.
(3) 10g beta-molecular sieve powder is added in 1000mL ammonium nitrate solutions (1.0mol/L), located under the conditions of 80 DEG C
Reason carries out ion exchange in 24 hours, fully washs and filters, and then repeats above-mentioned ammonium ion and exchanges 3 times, is dried at 120 DEG C
24h, after zeolite molecular sieve is calcined 4 hours under normal atmosphere pressure at 550 DEG C, obtain hydrogenation synthesis β zeolite molecules
Sieve；
(4) 35g copper acetates (Cu is dissolved in 3500g deionized waters2(CH3COO)4·H2O) 35g, it is 3.8 to obtain pH
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) from the aqueous solution, hydrogenation synthesis zeolite molecular sieve 300g is added,
After being stirred 2 hours at 80 DEG C, filtered, separation of solid and liquid；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40 DEG C
3500g pure water is cleaned, and filtering and cleaning is repeated, until the pH value of detergent remover is 6~7；Then, dried at 120 DEG C
Screening matter 12h, it is calcined 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, the beta-molecular sieve of copper modification is obtained, according to
In catalyst prepared by icp analysis result, copper (II) ion accounts for the 3.0% of total catalyst weight, i.e. copper load capacity is
3.0wt%；
(5) the copper modified molecular screen for taking 15g steps (4) to obtain, with the commercially available Ludox of 4.32g (silica quality content
For 20wt%) and 15.93g deionized waters are well mixed is fabricated to the catalyst slurry that solid content is 45.0 mass %, and by its
It is coated in by infusion process on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 105 DEG C, and SCR catalysis is prepared into after 2h is calcined under the conditions of 500 DEG C
Agent, the load capacity on regular material is 236.3g/L, is designated as VS-3.
Comparative example 4
The ZSM-5 molecular sieve selective reduction catalyst that a kind of copper is modified, is prepared by following methods：
(1) in 800g sodium silicate aqueous solution (mass fractions：SiO226%th, Na2O 7.0%) in addition sodium hydroxide it is water-soluble
Liquid (5g sodium hydroxides, which are dissolved in 400g deionized waters, to be prepared), the hexahydrate (Al of 61g aluminum sulfate ten is added while stirring2
(SO4)3·16H2O) 1, the 3- dimethyl ureas with l0g are dissolved in the aqueous solution being formulated in 1.5kg deionized waters, finally add
The sulfuric acid 1000g for adding mass fraction to be 5%, obtain uniform primary gel；
(2) autoclave that the gel described in step 1 is loaded to 5L produces self-generated pressure, under 200 revs/min of speed stirrings,
160 DEG C of crystallization 72 hours, obtain MFI kind crystalline substance zeolite molecular sieves；
(3) in 640g sodium silicate aqueous solution (mass fractions：SiO225%th, Na2O 8.0%) in add 1.75kg deionizations
Water, the hexahydrate (Al of 25g aluminum sulfate ten2(SO4)3·16H2O) and 35g sulfuric acid (mass fraction 97%), step is continuously added
(2) two level gel is obtained after the MFI kind crystalline substance zeolite molecular sieves 1.5kg stirrings obtained by；Two level gel is put into 5L autoclave
Self-generated pressure is produced, crystallization is stirred at 150 DEG C, 110 revs/min of mixing speed, processing time are 45 hours；The slurries that will be obtained
Filtering, washing, product is obtained after being dried 5 hours at a temperature of 120 DEG C；With the icp analysis product, it is known that wherein SiO2：A12O3
Mol ratio be 80：1, the XRD analysis product is the ZSM-5 molecular sieve for having MFI type structure；
(4) drying ZSM-5 molecular sieve 10g is taken to be added in the aqueous ammonium nitrate solution that 84.56ml concentration is 1.2mol/L；
The ion exchange of 3 hours is carried out at 70 DEG C, is then filtered, then is washed with the water of 5 times of amounts, then is done at a temperature of 120 DEG C
Dry 10 hours, then carry out being calcined for 2 hours at 550 DEG C, obtain Hydrogen ZSM-5 molecular sieve.
(5) 35g copper acetates (Cu is dissolved in 3500g deionized waters2(CH3COO)4·H2O) 35g, it is 4.8 to obtain pH
Copper acetate (II) deionized water solution；In above-mentioned copper acetate (II) from the aqueous solution, Hydrogen ZSM-5 zeolite molecular sieve is added
300g, after being stirred 2 hours at 80 DEG C, filtered, separation of solid and liquid；Hydrogenation synthesis zeolite molecular sieve after separation of solid and liquid is with 40
DEG C 3500g pure water clean, be repeated filtering and cleaning, until detergent remover pH value be 6~7；Then, dried at 120 DEG C
Dry filter material 12h, it is calcined 2 hours at 550 DEG C；After being classified with the mesh screen of 40 mesh, the ZSM-5 molecules of copper modification are obtained
Sieve, according in the catalyst of icp analysis result preparation, copper (II) ion accounts for the 2.90% of total catalyst weight, i.e. copper load capacity
For 2.90wt%；
(6) the copper modified molecular screen for taking 15g steps (4) to obtain, with the commercially available Ludox of 6.26g (silica quality content
For 20wt%) and 21.51g deionized waters are well mixed is fabricated to the catalyst slurry that solid content is 38.0 mass %, and by its
It is coated in by infusion process on the cellular porous regular material (#300cpsi, diameter 21mm, length 20mm) of cordierite system, with pressure
Contracting air blows unnecessary slurry droplet off, is dried 24 hours at 120 DEG C, and SCR catalysis is prepared into after 2h is calcined under the conditions of 550 DEG C
Agent, the load capacity on regular material is 241.6g/L, is designated as VS-4.
Embodiment 19~28
SCR catalyst is tested：
SCR catalyst (the size of the cellular material coating prepared in Example 1~6 and comparative example 1~4), in reactorIn, include 500ppm NO, 500ppm NH3,10 volume %O2,5 bodies
Product % steam and the mixed airflow 160mL/min that Ar is Balance Air, first pass through preheater (being set as 250 DEG C), subsequently into SCR
Reactor.In 100~550 DEG C of reaction temperatures and based on 48000h-1Sample is tested under volume gas hourly space velocity.The temperature
Degree passes through the interior thermocouple monitoring at sample position.
Each fresh SCR catalyst in used above-described embodiment and comparative example is carried out into the durable processing of hydro-thermal to be aged
SCR catalyst, hydro-thermal it is durable processing experiment condition be：
Space velocity SV：30000/h, temperature：800 DEG C, the time：16 hours, moisture concentration：10%, oxygen concentration：10%,
Nitrogen concentration：Balance.
After carrying out hydro-thermal ripening according to above-mentioned parameter, continue to be used for NOx catalytic reduction reactions as SCR catalyst
Evaluation test：
NO conversion ratios or " de- NOx " activity is under steady state conditions, a reactor by using the type FT-IR light of Bruker EQUINOX 55
Spectrometer measures NOx, NH3 and N2O concentration in exit and determined.
Using above-mentioned SCR catalyst activity laboratory evaluation device, the loaded Cu that embodiment and comparative example are prepared
SCR catalyst carry out NOx SCR performance evaluation, as a result as shown in table 4.
Table 4
Can as seen from Table 4 under all test temperatures, the Cu-AEI catalyst samples low temperature for preparing of the present invention and high temperature
SCR activity (comparing from NOx removal data) is substantially better than Cu-SSZ-13 in comparative example, Cu-SAPO-34, Cu- β and Cu-
ZSM-5 catalyst samples, no matter its " fresh " state or " ageing " state.Therefore, the result obtained by embodiment 19~24
Clearly show the Cu-AEI molecular sieve catalytics agent material of the present invention and with the catalyst of its acquisition there is improved SCR to be catalyzed
Under activity, especially low conversion temperature specific to the cold start in the application of such as diesel locomotive during processing NOx.With regard to it
For his SCR applications, Cu-AEI molecular sieve catalytic agent materials of the invention allow have higher conversion at lower temperatures
Rate, therefore allow higher efficiency and therefore under suitable conversion ratio, it is allowed to handle useless containing NOx energy-efficient
Gas, such as the waste gas obtained from commercial run.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.Without departing from the premise in the spirit of the present invention, all essence according to the present invention is made equivalent transformation, change or repair
Decorations, appended claims should all cover within the protection domain of spirit of the present invention.
Claims (13)
- A kind of 1. preparation method of Cu-AEI molecular sieve catalysts, it is characterised in that：Being used as using pyrroles/pyrrolidines material is had Machine template, it is silicon source and silicon source with FAU type Si-Al molecular sieves, other silicon sources can be combined, alkali source forms mixed sols, crystallization AEI type molecular sieves are synthesized, is loaded to Ni metal as metallic promoter agent on AEI type Si-Al molecular sieves, Cu-AEI is prepared Molecular sieve catalyst, slurries then are mixed into binding agent, loaded on porous regular material, may be used as NOx selectivity Catalysis reduction SCR catalyst.
- 2. according to the preparation method described in claim 1, it is characterised in that：Silica and aluminum oxide in AEI molecular sieves Molecule mol ratio is 0.5~5.0wt% that 10~300, Cu contents are Cu-AEI molecular sieve catalyst gross masses.
- 3. according to the preparation method described in claim 1, it is characterised in that：Cu-AEI molecular sieve catalyst preparation methods include：(1) by silicon source with SiO2Calculating, silicon source are with Al2O3Calculating, alkali lye are with Na2O is calculated and organic formwork agent OSDA is according to Na2O: SiO2:Al2O3:OSDA:H2O=0.1~0.5:1.0:0.0033~0.083:0.05~0.5:10~50 molar ratio is carried out It is mixed into colloidal sol shape；(2) mixture in (1) is transferred in crystallizing kettle and enters Mobile state and divide temperature section crystallization, first paragraph crystallization temperature section It it is 120~150 DEG C, crystallization time is 12~72 hours；Second segment crystallization temperature section is 170~200 DEG C of crystallization times for 12~ 96 hours；(3) molecular sieve that (2) crystallization obtains is reclaimed, then with copper ion salt in the range of pH value of solution=5.0~7.0, Room temperature degassing process under negative pressure, then at 60~100 DEG C dry 4~24 hours, then under normal pressure at 450~550 DEG C roasting 2~ 8 hours, obtain Cu-AEI molecular sieves.
- 4. according to the preparation method described in claim 2, it is characterised in that：Silicon source may come from white carbon, Ludox, water glass It is one or more in glass, alkyl silicate, macro porous silica gel, silochrom, Kiselgel A, Type B silica gel and tlc silica gel.
- 5. according to the preparation method described in claim 2, it is characterised in that：The FAU types Si-Al molecular sieve includes X and Y zeolites.
- 6. according to the preparation method described in claim 2, it is characterised in that：Organic formwork agent is selected from pyrroles/pyrrolidines thing Matter, including 1- hydroxyl -3,4- dimethyl pyrrolidines -2,5- diketone, 1- epoxides -2,2,5,5- tetramethylpyrrolidi-e -3- methyl first Alkane thiosulfonic acid, 1- epoxide -3- carboxyl -2,2,5,5- tetramethylpyrrolidi-es, 1,2,2,5,5- pentamethyls pyrrolidines, 1- (4- second Base -3,5- dimethyl -1H- pyrroles -2- bases)-ethyl ketone, 2,3,4,5- tetramethyls pyrroles, 1- isopropyl -2,3,4,5- tetramethyl pyrroles Cough up, 3,5- dimethyl -2- pyrrole aldehydes, 3,4,5- trimethyl -1H- pyrroles -2- methyl formates, 3,4,5- trimethyl -1H- pyrroles Cough up -2- Ethyl formates, 3- carboxyl -2,2,5,5- tetramethylpyrrolidi-e -1- oxygen radicals.
- 7. according to the preparation method described in claim 1, it is characterised in that：Mantoquita is copper nitrate, copper chloride, copper acetate or sulfuric acid One or more of in copper, the concentration of copper ion is 0.1~1.5mol/L in copper salt solution.
- 8. according to the preparation method described in claim 1, it is characterised in that：Binding agent can be Ludox, waterglass, intend thin water It is one or more in aluminium stone, Alumina gel.
- 9. according to the preparation method described in claim 1, it is characterised in that：Its porous regular material includes honeycombed, board-like shape Or corrugated regular carrier material, material are selected from cordierite, alph-alumine, carborundum, aluminium titanates, silicon nitride, zirconium oxide, Mo Lai Stone, spodumene, alumina-silica magnesia, zirconium silicate or sheet metal.
- 10. according to the preparation method described in claim 1, it is characterised in that：Carrier is that the cellular of porous cordierite flows through type Monolith carrier, its bearing capacity are 170~270g/L.
- 11. the application of the catalyst obtained according to preparation method described in claim 1, in a manner of being in fluid communication and connect, make bag Waste gas, reducing agent containing NOx are contacted with SCR catalyst composition, and at least a portion of the NOx is optionally reduced into N2 And H2O。
- 12. applied according to described in claim 10, the source of reducing agent can be selected from ammonia in itself, hydrazine or ammonia precursor, before the ammonia Body includes one or more in urea, ammonium carbonate, aminoquinoxaline, ammonium hydrogen carbonate or ammonium formate.
- 13. according to preparation method described in claim 1, it is characterised in that：Tail gas containing NOx includes the waste gas of vehicular emission Stream.
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